Antistatic additive compositions

ABSTRACT

Antistatic compositions comprising 1. OLEFIN-SULFUR DIOXIDE COPOLYMER CONSISTING ESSENTIALLY OF UNITS DERIVED FROM SULFUR DIOXIDE, C6 1-alkene, and optionally an olefin having the formula     WHEREIN A is a group having the formula -(CxH2x)-C00H wherein x is from 0 to about 17, and B is hydrogen or carboxyl, and 2. A QUATERNARY AMMONIUM COMPOUND. D R A W I N G

United States Patent 1191 l2/l96l Vander Minne et al 44/DIG. 2

Johnson May 21, 1974 ANTISTATIC ADDITIVE COMPOSITIONS Primary Examiner-Daniel E. Wymzin Assistant ExaminerY. H. Smith I l D. h N D l. [75] mentor Jo ewdrk e Attorney, Agent, or Firm-James A. Costello; Nlcholas [73] Assignee: E. l. du Pont de Nemours and J Masington, Jr.

Company, Wilmington, Del.

[21] Appl' 2685045 Antistatic compositions comprising 1. olefin-sulfur dioxide copolymer consisting [52] US. Cl 44/62, 44/72, 44/76, essentially of units derived from sulfur dioxide,

44/80, 44/DIG. 2 C,; 1-alkene, and optionally an olefin having the [51] Int. Cl C101 1/24 formula [58] Field of Search 44/62, 68, 76 H A B [56] References Cited c=o, UNITED STATES PATENTS H 3,256,073 6/196 Hess 44/62 2,683,156 7/l954 ller 106/287 2,273,040 2/1942 1161 260/414 Wherem A 15 a P haYmg the formula 3,442,790 5/1969 8611 m et al 44/62 .r 2.r)"" wherein x 1s rom 0 to about 3,013,868 12/1961 Skei et al... 44/62 17, and B is hydrogen or carboxyl, and 3,126,260 3/1964 Vander Minne et al...; 44/62 -2 a quaternary ammonium compound.

10 Claims, No Drawings ANTISTATIC ADDITIVE COMPOSITIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to novel antistatic compositions of olefin polysulfones and quaternary ammonium compounds, and hydrocarbon fuels made conductive for prolonged periods by admixture with said antistatic compositions.

2. Description of the Prior Art r The accumulation of electrical charges in thehandling of hydrocarbon fuels is widely'recognized in the art as a serious hazard. Spark discharge over flammable fuels because of'the accumulation of static electrical charge in the fuels has been considered responsible for numerous explosions and fires. The accumulation of static electrical charge is believed to occur during the movement of hydrocarbon fuels in contact with other substances such as pipes, filters or water. Since the hy-' drocarbon fuels are normally very poor conductors of electricity, the charge in the fuel is not rapidly dissipated and, where such accumulation of electrical charge reaches a sufficiently high level, the electrical energy is discharged as sparks which can ignitehydrocarbon vapors present in admixture with the air thus causing an explosion or fire.

Procedures undertaken tominimize the explosion hazards caused by static electricity, e.g., grounding of the equipment or blanketing of fuels with inert gas and the modifications in the mechanical handling of the fuels have been of limited value. It is generally recognized in the art that the most practical and promising approach to overcoming the problem is use of a conductivity additive (antistatic additive) in the fuels such that the conductivity characteristics of the hydrocarbon fuel are increased thus preventing the accumulation of a high level of electrical charge within the fuel. It is also generally recognized that when the hydrocarbon fuel has a conductivity of at least about 50 picomhos per meter the danger is reduced, and such hydrocarbon fuel may be safely handled, although often a preference is expressed for a conductivity of at least 200 picomhos per meter to provide additional margin of safety.

Numerous materials have been suggested in the art for use in increasing the electrical conductivity of hydrocarbon fuels. The conductivity additives suggested are generally polyvalent metla organic salts of metals of atomic number of from about 12 to about 29 of the Periodic Table. Since electrical conductivity depends upon the presence of ions, the antistatic additives are almost always ionic compounds. Thus Minne et al. in U.S. Pat. No. 3,012,969 have suggested a combination of calcium or chromium diisopropyl salicylate with other salts, such as salts of dialkylsulfosuccinate. Hess in U.S. Pat. No. 3,256,073 discloses liquid hydrocarbons which contain organic metal salts of carboxylic, phosphoric and sulfonic acids together with organophosphate salt of basic aminoalkylacrylate polymer. Skei et al. in U.S. Pat; No. 3,013,868 disclose a conductivity additive composition comprising an aromatic acid salt of a metal having an atomic number from 22-28 and a nitrogen-containing copolymer. The purpose of the nitrogen containing copolymer is to improve the retention of conductivity values over a longer period of time.

It is recognized that a conductivity additive composition must not only increase the electrical conductivity of the substrate fuel but should in addition l maintain the increased conductivity over a sufficiently long period of time to allow for transportation and storage of fuels and (2) be resistant to removal from the fuel when brought into contact with water, and (3) should not affect the ability of the fuel to separate from water. The prior art conductivity additives are known to be deficient in that they lack one or more of the above requirements. It is known that salts are useful in increasing conductivity initially, they gradually lose conductivity over a period of time (cf. U.S. Pat. No. 3,013,868, col. 2, lines 24-27). When the hydrocarbon fuels are, as is frequently the case, unavoidably exposed to water during storage or during transportation 1 the conductivity additive may be extracted into the water phase thus depleting the protection afforded by the additive to the hydrocarbon phase or (2) the ability of the fuel to separate itself from water is changed, disturbing the efficiency of water separation process, such that the hydrocarbon fuel will contain undesirable amount of water.

Novel antistatic compositions have now been discovered which (1) confer increased conductivity of a prolonged nature to hydrocarbon fuels, (2)are resistant to removal from the fuel when brought in contact with water and (3) do'not affect the water separation index of the-hydrocarbon fuels and are ashless.

SUMMARY OF THE INVENTION This invention is directed to antistatic compositions 1 comprising (1) a polysulfone copolymer consisting essentially of about 50 mol percent of units derived from sulfur dioxide, from about 40 to 50mol percent of units derived from l-alkene of 6 to 24 carbon atoms and optionally from 0 to about 10 mol percent of units derived from an olefin having the formula wherein R and R are the same or different alkyl groups having from 1 to 22 carbon atoms; R is selected from the group consisting of alkyl groups having from I to 22 carbon atoms and Amino)...

groups wherein R is hydrogen or methyl and n is from 1 to 20; and R is selected from the group consisting of:

a. an alkyl group having from 1 to 22 carbon atoms;

b. an aralkyl group having from 7 to 22 carbon atoms;

imam)...

group wherein R and R are the same or different alkyl groups having from 1 l to 19 carbon atoms; and

e. an R -CO group wherein R is a hydrocarbyl group having from 1 to 17 carbon atoms;

with the proviso that when R, R R and R are each alkyl groups, at least one of R, R R and R is an alkyl group having at least 8 carbon atoms; A is an anion; z is 0 or 1 and when R is (d) or (e), z is 0; y is at least one and when 2 is l, y is numerically equal to the ionic valence of anion A.

DESCRIPTION OF THE INVENTION The antistatic compositions of this invention consist essentially of l) polysulfone copolymer derived from the copolymerization of sulfur dioxide with l-alkene of 6 to 24 carbon atoms and an optional olefin having the formula indicated above, and (2) a quaternary ammonium compound.

Also included within the scope of this invention are liquid hydrocarbon fuels of high electrical conductivity consisting essentially of a hydrocarbon boiling in the range of 70F. to about 700F. and the antistatic composition as defined above'in an effective antistatic amount. The weight ratio of the polysulfones copolymer to the quaternary ammonium compound is from about [00:1 to about 1:100. Polysulfones The polysulfone copolymers useful in the invention are copolymers consisting essentially of about 50 mol percent of units derived from (1) S0 i.e., sulfur dioxide, from about 40 to about 50 mol percent of units derived from (2) CH =CHR, wherein R is an alkyl group of from about 4 to 22 carbon atoms, i.e., l-alkenes of about 6 to 24 carbon atoms and optionally from 0 to about mol percent of units derived from an olefin having the formula:

wherein A is a group having the formula -(C,H

)COOH wherein x is from 0 to about 17 and B is hydrogen or carboxyl with the proviso that when B is carboxyl, x is 0 and wherein A and B together may be a dicarboxylic anhydride group. The polysulfone copolymers, often designated as olefin-sulfur dioxide copolymer, olefin polysulfones, or poly(olefin sulfone) are linear polymers wherein the structure is considered to be that of alternating copolymers of the olefins and sulfur dioxide, having a one-to-one molar ratio of the comenomers with the olefins in head to tail arrangement. Since the polysulfones are inexpensive and are usually light-colored, amorphous, readily moldable and extrudable, considerable effort has been expended to prepare new types or to improve the properties of the polymer for a general use as a thermoplastic polymer. The polysulfones used in this invention are readily prepared by the methods known of the art (of. Encyclopedia of Polymer Science and Technology Vol. 9, Interscience Publishers, page 460 et seq.). The reaction leading to polysulfone formation is considered to be a free radical polymerization process. Almost all types of radical initiators are effective in initiating polysulfone formation. Radical initiators such as oxygen, ozonides, peroxides, hydrogen peroxide, ascaridole, cumene peroxide, benzoyl peroxide, azobisisobutyronitrile are examples of some of the useful initiators. Polysulfone formation can also be initiated by irradiation with visible light. While polysulfones prepared by any of the methods of the art are useful in the present invention, the preferred product is that prepared by ultra-violet light induced polymerization of l-alkene and sulfur dioxide in the presence of azobisisobutyronitrile in a solvent such as toluene with a small amount of dodecyl mercaptan (from about 0.002 to 0.03 mole per mole of olefin) as a molecular weight modifier. The weight average molecular weight of the polysulfones useful in this invention is in the range from about 10,000 to about 1,500,000 with the preferred range being from about 50,000 to about 900,000 and the most preferred molecular weights being in the range of from about 100,000 to about 500,000. Olefin polysulfones whose molecular weights are below about 10,000, while effective in increasing conductivity in hydrocarbon fuels, do not appear to increase the conductivity values as much as olefin polysulfones of higher molecular weights. Olefin polysulfones whose molecular weights are above about 1,500,000 are difficult to produce and are more difficult to handle. The molecular weights of the olefin polysulfones may be determined by any of the well known methods, such as the light scattering method. It is generally more convenient, however, to determine the inherent viscosity of the polymer to derive the approximate molecular weight range of the polysulfones therefrom. Inherent viscosity is defined as m in.

A ,,.,/C wherein In is the natural logarithm, 17 rel is a relative viscosity, i.e., ratio of the viscosity of the polymer solution to the viscosity of the polymer solvent and C is concentration of polymer in g./ ml. The units of inherent viscosity are deciliters per gm. The inherent viscosities of olefin polysulfones are conveniently measured in toluene at 30C. as 0.5 weight percent solutions. It has been found by comparison with molecular weight determinations that olefin polysulfones with inherent viscosities of between about 0.1 dl/g to about 1.6 dl/g correspond to weight average molecular weights in the range of about 50,000 to about 900,000. The control of the molecular weights of the olefin polysulfones in the desired range is readily accomplished by those skilled in the art of polymer science by controlling the polymerization conditions such as the amount of initiator used, polymerization temperature and the like or by using molecular weight modifiers such as dodecyl mercaptan. The amount of molecular weight modifier required to obtain the desired molecular weight range will depend upon the particular l-olefin being polymerized with sulfur dioxide, however the requisite amount can be readily determined with few experiments. Generally the amount of modifier, such as dodecyl mercaptan, used to obtain the molecular weights in the range of 50,000 to 900,000 is in the range of up to about 0.007 mole per mole of l-olefin.

The olefins useful for the preparation of the polysulfones are l-alkenes of about 6 to 24 carbon atoms. The l-alkenes are generally available commercially as pure or mixed olefins from petroleum cracking process or from the polymerization of ethylene to a low degree. The useful l-alkenes include for example l-hexene, 1- heptene, l-octene, l-nonene, ldecene, l-undecene, l-dodecene, l-tridecene, l-tetradecene, lpentadecene, l-hexadecene, l-heptadecene, 1- octadecene, l-nonodecene, l-eicosene, l-heneicosene, l-docosene, l-tricosene and l-tetracosene. While the normal straight chain l-alkenes are preferred, it is understood that l-alkenes containing branched chains are also useful. It is also understood that a mixture of lalkenes may be used and may often be desirable since a mixture of 'l-alkenes are often obtainable at a lower cost than are pure olefins. The olefin portion of the polysulfone should be an olefin of at least 6 carbon atoms to insure that thepolysulfone is sufficiently soluble in hydrocarbons. For practical and economic reasons, the olefin used for the preparation of polysulfone should have less than about 24 carbon atoms. The preferred olefins will have from about 8 to about 12 carbon atoms, the most preferred olefin having carbon atoms, i.e., l-decene polysulfone.

The olefin polysulfones of the invention may also optionally contain in copolymerized form 0 to 10 mol percent of an olefin of the formula wherein A is a group represented by the formula (C,H ,)COOl-lwherein x is 0 to 17 and B is selected from the group consisting of hydrogen and carboxyl with the proviso that when B is a carboxyl then x is 0, and wherein A and B taken together may be a dicarboxylic anhydride group. When maleic anhydride is copolymerized with a l-olefin and sulfur dioxide, the resulting copolymer will contain the dicarboxylic anhydride group. The dicarboxylic anhydride group in the polymer is readily converted to two carboxyl groups by simple acid hydrolysis. In the olefin of the formula when B is hydrogen, the olefin will be a terminally unsaturated alkenoic acid represented by 6 CH =CH(C,l-ll )-COOH. The alkylene group bridging the vinyl and the carboxyl groups will have from 1 to 17 carbon atoms or it may be absent, and such alkylene group when present may be straight chain group or branched chain. The useful acids are alkenoic acids of 3 to 20 carbon atoms wherein the olefinic group is a terminal group. Representative but nonlimiting examples of alkenoic acids with a terminal olefinic group include acrylic acid, 3-butenoic acid, 4-pentenoic acid, S-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8- nonenoic acid, 9-decenoic acid, IO-undecenoic acid, 1 l-dodecenoic acid, l3-tetradecenoic acid, 15 hexadecenoic acid, .l7-octadecenoic acid as well as branched chain alkenoic acids with terminal olefinic groups such as 2-ethyl-4-pentenoic acid, 2,2-dimethyl- 4-pentenoic acid, 3-ethyl-6-heptenoic acid, 2-ethyl-6- heptenoic acid, 2,2-dimethyl-6-heptenoic acid and the like. It is also understood that a mixture of alkenoic acids may be used.

While olefin polysulfones, as described are effective conductivity increasing additives in hydrocarbon fuels, it has been found that in certain fuels, in order to obtain the desired high initial or instantaneous conductivity,

'of approximately 200 picomhos per meter, relatively large amounts of olefin polysulfones are required. Since the hydrocarbon fuels treated with olefin polysulfones have the unusual characteristics of continuing to increase in conductivity with time, the treated hydrocarbon fuels will, after a period of time, have conductivities of up to about seven times the initial conductivities. In order to minimize the treating cost, it is desirable to minimize the amount of the additive required to produce the desired effect. In other words, it is desirable to provide a conductivity additive which can impart high conductivity to the fuel instantaneously and maintain a high conductivity level for long periods of time.

It has now been found that a combination of olefin polysulfone and a quaternary ammonium compound, at

very low concentrations, provide high initial conductivity as well as long-lasting conductivity. Concentrations as low as a few tenths of part per million (ppm) have been found sufiicient to demonstrate increased conductivity. It is wholly unexpected and surprising that the combination of olefin polysulfone and quaternary ammonium compound exhibits conductivity significantly greater than that attributable to each of the individual components of the combination and that the conductivity of the treated fuels continues to increase with time. Quaternary Ammonium Compound The quaternary ammonium compounds found to be useful in the present invention have the general formula:

R: [R -I I-R h) R3 (y) V wherein R and R are the same or different alkyl groups having from 1 to 22 carbon atoms; R is selected from the group consisting of alkyl groups having from 1 to 22 carbon atoms and Rs (CH2CHO H groups wherein R is hydrogen or methyl and n is from 1 to 20; and R is selected from the group consisting of:

chasm)...

group wherein R is hydrogen or methyl and n is from 1 to 20; d. a

group wherein R and R are the same or different alkyl groups having from l l to 19 carbon atoms; and

e. A R"CO group wherein R is a hydrocarbyl group having from 1 to 17 carbon atoms;

with the proviso that when R, R R and R are each alkyl groups, at least one of R R R and R is an alkyl group having at least 8 carbon atoms; A is an anion; z is 0 or 1 and when R is (d) or (e), z is 0; y is at least one and when 2 is l, y is numerically equal to the ionic valence of anion A.

Useful quaternary ammonium compounds wherein R, R R and R are alkyl groups are tetraalkyl ammonium salts. Examples of alkyl radical and aralkyl radicals coming within the definition of R, R R and R include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, octadecenyl, octadecadienyl, octadecatrienyl, mixtures of hydrocarbon radicals derived from tall oil, tallow, soy bean oil, coconut oil, cottonseed oil and other oils of vegetable and animal origin as well as aryl-substituted alkyl radicals such as benzyl, phenylethyl, phenylpropyl and the like. The tetraalkyl quaternary ammonium salts are readily available, either commercially or by preparation by art known methods. For example, certain useful tetraalkyl ammonium salts are sold by Armour (Chicago, Illinois) under the tradename of Arquad" such as Arquad" ZHT-T (dimethyldihydrogenated tallow quaternary ammonium chloride), Arquad 2S (dimethyldisoya quanternay ammonium chloride), Arquad" ZHT Nitrite (dimethyldihydrogenated tallow quaternary ammonium nitrite), Arquad" 2C chloride (dicocodimethyl ammonium quaternary chloride) and Arquad 2C- Nitrite (dicocodimethyl ammonium quaternary nitrite).

The quaternary ammonium compounds are also readily prepared by known procedures, e.g., treating an amine with alkyl halide, aralkyl halide, alkyl sulfate and the like as exemplified by the equation, RNH +3RCl RN(R') Cl+2HCl. The starting amine may be a primary amine as exemplified in the above equation, or may be a secondary or a tertiary amine. For convenience, a tertiary amine is usually preferred. The amines useful for the preparation of the quaternary ammonium compounds of the invention are generally available commercially. Particularly useful amines are tertiary amines derived from vegetable and animal oils which are sold by Armour and Company (Chicago, lllinois) under the tradename of Armeen such as Armeen DM12D, Arrneen" DM14D, Armeen" DMl6D, Armeen DM18D, Armeen DMCD, Armeen DMSD, Armeen" DMHTD and Armeen M2HT. The code for the above amines is DM for dimethyl, M for methyl, CD for distilled coconut oil amine, SD for distilled soybean oil amine, 2HTD for distilled dihydrogenated tallowamine and the 12D, 14D, 16D and 18D are distilled fatty amines containing predominantly the number of carbon atoms in the code number. 1

Representative but non-limiting examples of useful tetraalkyl quaternary ammonium salts include in addition to the above-listed Arquads, dioctadecyldimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, dodecyltrimethyl ammonium chloride, the C C alkyl trimethyl ammonium chlorides, the di-C C alkyldimethyl ammonium chlorides, hexadecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium iodide, dioctadecyldimethyl ammonium bromide, dioctadecylmethyl benzyl ammonium chloride, octadecyldimethylbenzyl ammonium chloride, oxtadecyldimethyl(phenylethyl) ammonium chloride and the like. Similarly, nitrites, sulfates, alkylsulfates, phosphates, carboxylates corresponding to the above quaternary ammonium halides may be used. The preferred salt of this type is dicocodimethyl ammonium nitrite wherein coco" is a mixture of C C alkyl radicals of cocoamine.

The useful quaternary ammonium compounds include those wherein R and R in the general formula given previously are groups, wherein R and n are as defined These compounds are readily prepared by the reaction of a primary amine with 1,2-alkylene oxide such as ethylene oxide and 1,2-propylene oxide. The number of alkylene oxide units attached to the amine is readily detennined by the ratio of the reactants used. As is known in the art, a mixture of alkylene oxides such as that of ethylene oxide and propylene oxide may be used to obtain an amine derivative wherein the polyoxyalkylene group attached to the nitrogen atoms are composed of a random mixture of alkylene oxide units or the condensation reaction may be carried out in steps, whereby the polyoxyalkylene group is derived from one alkylene oxide and by then continuing the reaction with another alkylene oxide to obtain polyoxyalkylene substituent groups in which the polyoxyalkylene units are present as blocks. The amine with the polyoxyalkylene group may be quatemized by reaction with alkyl halides, alkyl sulfate, etc., as described above. In view of the above description, the R group may be independently hydrogen or methyl in each of the n units.

The anion, A, of the quaternary ammonium compounds may be any anion of a salt forming acid. Such anions include chloride, bromide, iodide, sulfate, bisulfate, alkylsulfate, arylsulfate, alkanesulfonate, arenesulfonate, nitrate, nitrite, phosphate, monoalkyl phosphate, dialkyl phosphate, monoaryl phosphate, diaryl phosphate, borate, carboxylate and the like. The preferred anions are halides and nitrite.

The quaternary ammonium compounds wherein the i R group is wherein R and R may be the same or different alkyl groups having from about 11 to 19 carbon atoms are also useful in the present invention. This class of compounds known as phospholipids or lecithins are well known in the art and have been used in petroleum products as non-metallic sludge dispersants in lubricating oils. Naturally occurring lecithin is having the formula wherein the R groups are derived from stearic, oleic, linoleic and arachidonic acids. While lecithins are commerically available, if desired, suitable lecithins may be readily prepared by the reaction involving esterification of glycerol with two moles of fatty acid halide, reaction of the glycerol diester with phosphorous oxychloride to form diacylglycerophosphoryl chloride which is then reacted with a 'cho1ine-type compound to form the lecithin. The acyl group of the fatty acid halide is chosen so that the lecithin will be sufficiently soluble in hydrocarbon fuels.

Suitable fatty acid halides are those derived from carboxylic acids having about 12'to20 carbon atoms such as dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecanoic, heptadecanoic, octadecanoic, nonadecanoic and eicosanoic acids. The use choline-type compounds are those having the formula wherein R", R and R are as previously defined. The R, R and R groups are preferably alkyl groups having from 1 to 4 carbon atoms, more preferably the R R ,.and R groups are methyl groups.

Quaternary ammonium compounds where R is an R CO group are also useful in the present invention. This class of quaternary ammonium compounds which are dipolar ions, may be referred to generally as betaines. Useful betaines are disclosed in US. Pat. No.

While certain quaternary ammonium compounds are known in the art as useful antistatic agents in hydrocar bon fuels, it has now been found that a combination of the above-described-olefin polysulfone and quaternary ammonium compounds is particularly effective for increasing the electrical conductivity of hydrocarbon fuels and, moreover, the effect of the combination is considerably greater than is expected based on the effect exhibited by each individual component. It has also been found that'the conductivity imparted to hydrocarbon fuels is longlasting and in most fuels, continues to increase such that after a few weeks the conductivity may be several tiines greater than the initial conductivity.

The ratio of olefin polysulfone to quaternary ammonium compound may be from about 100:1 to about 1:100, preferably in the range of from about 50:1 to about 1:1, most preferably in the range of from about 20:1 to about 1:1. The most preferred ratios afford compositions which are economical to use, are effective in increasing conductivity and do not adversely affect other desirable characteristics of the hydrocarbon fuels. Te preferred olefin polysulfone to be used in this invention is l-decene polysulfone having an inherent viscosity in the range from about 0.1 dl/g. to 1.6 gl/g. (M.W. of 50,000 to 900,000), and the preferred quaternary ammonium compound is dicocodimethylammonium nitrite.

The amount of the invention compositions to be added to the hydrocarbon fuels will depend upon the combination chosen, the electrical conductivity desired and the particular hydrocarbon fuel. It is recognized that the electrical conductivity of liquid hydrocarbons will vary depending upon the particular source of the hydrocarbon and its processing history. Usually the hydrocarbon fuels in the gasoline boiling range have very low conductivities (0-10 picomhos/meter) while those in the fuel oil range have somewhat higher conductivities (20-30 picomhos/meter). It is also recognized that the response of hydrocarbon fuels to conductivityincreasing additives may also vary unpredictably. Generally when the compositions of the invention are added to hydrocarbon fuels at a level as low as a few tenths of a part per million (ppm), increased conductivity is evident. In responsive fuels, concentrations of 1 to 10 parts per million are sufficient to give initial conductivities greater than 200 picomohos per meter whereas in poorly responsive fuels, concentrations greater than 10 parts per million may be required. Since as mentioned earlier, a hydrocarbon conductivity of 50 picomhos' per meter is considered to be sufficient for safe handling (or 200 picomhos/meter for an extra margin of safety), usually a sufficient amount of the compositions of the invention is added to the hydrocarbon fuel to obtain the initial conductivity of 50 picomhos/meter (or 200 picomhos/meter, if desired), although greater amounts may be used.

The mechanisms whereby the use of the additive compositions of the invntion provide unexpectedly high initial conductivities in hydrocarbon fuels and whereby the conductivities continue to increase with time are not known. While the present invention is not predicted upon any particular theory-or explanation, it may be that the increased conductivity may be dependent upon the possible unique ability of the olefin polysulfone to alter the characteristics of the ionic compounds. It is probable that in highly hydrophobic, lowdielectric media such as hydrocarbon fuels, dissolved quaternary ammonium compounds provide fewer dissociated ions than expected, in contrast to the situation in a highly polar, high-dielectric medium such as water wherein the dissolved quaternary ammonium compounds are believed to be completely dissociated. The presence of fewer than expected number of ions may be due to the lesser degree of dissociation or, more probably, due to the formation of ion aggregates or micelles which effectively reduces the number of particles available to conduct electrical charges, and thus the full potential of a quaternary ammonium compound as a conductivity increasing additive is not realized.

It may be further speculated that the olefin polysulfone provides an agent for either increasing the degree of dissociation of the quaternary ammonium compound or for breaking the micelles into smaller fragments such that more micelles are available to conduct electrical charges. The olefin polysulfone, because of the presence of recurring sulfone groups which can polarize, may be sufficiently polar to effect an increase in the number of charge-carrying particles. The continual increase in conductivity of hydrocarbon fuel treated with the combination of the invention may also be explained on the basis of either continual fragmentation of the micelles into smaller and smaller micelles or additionally on the basis that the olefin polysulfone may also complex with metal ions that may be present, such olefin polysulfone-metal ion complex then providing conductivity. The metal ions, which may be present as finely dispersed metal compounds (such as oxides) in the hydrocarbon fuels or as oxide coatings on metal surfaces of containers, pipelines, storage tanks, etc. are generally not available for conducting electrical charges because of the formation of aggregates or because of adherence ot the metal surfaces.

The above suggests that the olefin polysulfone should enhance the electrical conductivity of hydrocarbon liq uids treated with any ionic conductivity increasing additive wherein the full potential of such additive is not realized due to incomplete dissociation or due to the formation of micelles.

The normally liquid hydrocarbon fuels to which the compositions of the invention are added to render such hydrocarbon fuels electrically conductive are those boiling in the range of about 70 to 700F., and include such commonly designated fuels as aviation gasolines, motor gasolines, jet fuels, naphtha, kerosene, diesel fuels and distillate burner fuel oils. The compositions may be added to the hydrocarbon fuels in any convenient manner. Each individual component of the composition may be added to the hydrocarbon fuels sepa-' rately or the composition may be added as a simple mxture or as a solution in a solvent such as benzene, toluene, or xylenes, and stirred to obtain a uniform distribution. Generally, since it is preferable to prepare the olefin polysulfones in the presence of solvents such as those listed above, it is more convenient to add the olefin polysulfone as a solution in the solvent in which it is prepared. The concentrations of olefin polysulfones in the solvent may conveniently be in the range of from about percent by weight to about 60 percent by weight. The quaternary ammonium compound may be added to the olefin polysulfone solution so that the resultant composition may be added to the hydrocarbon fuels as a solution. The hydrocarbon fuel compositions containing one or more compositions of the invention as antistatic additive may also contain conventional additives used in hydrocarbon fuels such as antiknock compounds, antioxidants, corrosion inhibitors, metal deactivators, rust preventatives, dyes, anti-icing agents and the like.

EXAMPLES The following examples are intended to be merely illustrative of the invention and not in limitation thereof.

Unless otherwise indicated, all quantities are by weight.

In these examples, all conductivity measurements were made with a Maihak Conductivity Indicator (H. Maihak A.G., Hamburg, Germany). In operation the device imposes a potential of 6 volts of direct current on a pair of chromium plated electrodes immersed in the fluid to be tested. The current resulting from this potential, which is of the order of 10" to 10' ampere, is amplified and used to actuate a dial calibrated in conductivity units. A conductivity unit is l picomho per meter.

Example 1 This example describes the preparation of l-decene polysulfone. A 3-liter resin flask equipped with a stirrer, a reflux condenser, a thermometer and a gas inlet tube was swept with dry nitrogen. To the flask were added 400 g. l-decene, 1,430 g. toluene, and 2.8 g. dodecyl mercaptan. The contents of the flask were a solution which was cooled to between 5C. and 10C., and 200 g. of sulfur dioxide was passed into the solution. Azobisisobutyronitrile, 2.8 g., was then added and a mercury arc lamp was used to irradiate the solution. The stirred charge was kept at from 50 to 15C. with the sulfur dioxide being added continuously at such a rate that it was always in excess. At intervals of 4, 8, l2, and 16 hours, additional 1.4 g. portions of azobisisobutyronitrile were added. After a total of 20 hours of irradiation, the mercury lamp was turned off, the addition of sulfur dioxide was stopped, and nitrogen gas was passed into the viscous solution to remove excess sulfur dioxide. After the removal of the sulfur dioxide, a clear viscous solution weighing 1,820 g. was obtained. A weighed portion of the solution was removed and upon removal of toluene and unreacted l-decene by evaporation in a rotary vacuum evaporator, l-decenepolysulfone was obtained and identified by infra-red spectroscopy and elemental analysis. The Yield of ldecene polysulfone based on the above-isolated polymer was 279 g. (82%). The l-decene-polysulfone had an inherent viscosity of 0.36 measured as a'0.5 percent solution in toluene at 30C. The weight average molecular weight of the polymer as determined by light scattering method was 400,000.

EXAMPLES 2 18 Using the same procedure described in Example 1, other l-olefin polysulfones were prepared. Some of the l-olefin polysulfones with their inherent viscosities are summarized below.

Example Olefin Used Inherent Viscosity As measured in toluene at 30C as 0.5% solution.

EXAMPLE 19 This example describes the preparation of a polysulfone containing 50 mol per cent of sulfur dioxide, 45.5 mol percent of l-decene and 4.5 mol percent of maleic anhydride. A l-liter resin flask equipped as described in Example 1 was charged with 140 g. l-decane, 10 g. maleic anhydride, 1 g. dodecyl mercaptan and 300 g. toluene. The contents of the flask were a solution which was cooled to between 5C. and C. and 80 g. of sulfur dioxide was passed into the solution. Azobisisobutyronitrile, 1 g., was then added and a mercury arc lamp was used to irradiate the solution. The stirred charge was kept at 5 10C. with sulfur dioxide being added continuously at such a rate that it was always in excess. At intervals of 4, 8, l2, and 16 hours, additional of IO-undecenoic acid was prepared.

EXAMPLE 22 This example shows the unexpectedly high conductivity obtained when l-decene polysulfone of Example I is used together with dicocodimethyl ammonium nitrite in Bayol" (Bayol" is a standard reference jet fuel used in the industry for such purposes as determining water separation characteristics and corrosion inhibition). The olefin polysulfone was used as a percent solution in xylene while the dicocodimethyl ammonium nitrite was the commerically available Arquad" 2C-70 Nitrite, a 70 percent solution in isopropanol. The conductivity results are summarized in Table I below.

TABLE I CONDUCTIVITY OF l-DECENE POLYSULFONE ARQUAD" 2C-N1TRITE COMPOSITION 30% solution of l-dccene polysulfone in xylene. 70% dicocodimethylammonium nitrite in isopropanol. conductivity units.

0.5 g. portions of azobisisobutyronitrile were added.

turned off and the addition of sulfur dioxide stopped. The excess sulfur dioxide was removed by passing nitrogen into the viscous solution. A 20 g. portion of the solution was dried to give 7.1 g. of the polymer. The total solution therefore contained 165 g. (77.5 percent yield) of the polymer. The inherent viscosity of the polymer was 0.68. The presence of maleic anhydride in the polymer was demonstrated by infrared spectroscopy. Ey using the same procedure as described above, l-decene-maleic anhydried-sulfur dioxide copolymers containing l 47.6 mol percent l-decene, 2.4 mol percent maleic anhydride and 50 mol percent sulfur dioxide, and (2) 41.7 mol percent l-decene, 8.3 mol percent maleic anhydride and 50 mol percent sulfur dioxide were prepared.

EXAMPLE 20 Using the same procedure as described in Example 19 a polysulfone containing 50 mol percent of sulfur dioxide, 47.6 mol per cent of l-decene and 2.4 mol per cent of allylacetic acid (4-pentenoic acid) was prepared.

EXAMPLE 21 Using the same procedure as described in Example 19, a polysulfone cotaining 50 percent of sulfur dioxide, 47.6 mol per cent of l-decene and 2.4 mol per cent The data in this table clearly indicate unexpectedly After 20 hours of irradiation, the mercury arc lamp was 4 high conductivity for l-decene polysulfone in combination with dicocodimethylammonium nitrite. It can be seen for example that whereas l-decene polysulfone alone at 1.2 ppm gives a conductivity of 20 C.U. and dicocodimethylammonium nitrite alone at 11.6 ppm gives a conductivity of 40 C.U., the combination of ldecene polysulfone at 1.2 ppm with dicocodimethylammonium chloride at 11.6 ppm gives a conductivity which is not 60 C.U. (the sum of the individual conductivities) but 500 C.U.

EXAMPLE 23 This example shows the unexptected conductivies effected by various compositions of l-decene polysulfone and dicocodimethylammonium salts having different anions. The polysulfone was a 25 pprcent solution of l-decene polysulfone in toluene. The chloride salt was Arquad 2C-50 chloride (50 percent solution of dicocodimethylammonium chloride in isopropanol). The acetate was prepared by adding the required amount of sodium acetate to Arquad 2C-50 chloride, and filtering off the precipitated sodium chloride, while the petroleum sulfonate was prepared by adding sodium petroleum sulfonate (technical grade) to Arquad 2C-SO chloride and filtering off sodium chloride. The conductivity results are shown in Table ll below.

TABLE I1 CONDUCTIVITY OF I-DECENE POLYSULFONE WITH OUATERNARY AMMONIUM SALTS EXAMPLE 24 This example shows the increased conductivity effected by a composition of olefin polysulfonate containing a second olefinic component and a quaternary compound. The olefin polysulfone was l-decenemaleic anhydride-sulfur dioxide terpolymer of Example 19, and used as a percent solution in toluene while the quaternary ammonium compound was Arquad 2C Nitrite as a 70 percent solution in isopropanol. The

olefin polysulfone solution and the quaternary ammo- 25 nium compound solution was mixed in the ratio of 25:1 and thus the composition additive solution contained 24 percent of the polysulfone and 2.7 percent of the quaternary ammonium compound. The results of the conductivity measurements in three different fuels are shown below in Table III.

These results show that unexpected conductivies are obtained when an olefin polysulfone containing a second olefinic component is combined with a quaternary ammonium compound. In each of the fuels, the conductivities obtained by the use of the resulting composition are considerably greater than those anticipated on the basis of the individual components thereof. For example, in A-5, one would expect that the conductivity of the composition would be about 6-7 conductivity units based on A-1 and A-3; however, a conductivity of 70 C.U. is obtained.

Similar results are obtained with olefin polysulfones of Examples 20 and 2l.

EXAMPLE 25 This example shows the increased conductivity effected by a composition of an olefin polysulfone and a quaternary ammonium compound containing two polyoxyalkylene groups as substituents on the quaternary nitrogen. Quaternary ammonium compounds were prepared by condensing tallowamine with ethylene oxide followed by further condensation with 1,2-propylene oxide, both under basic conditions. The number of alkylene oxide units incorporated is determined by the molar ratio of the alkylene oxide to the amine. The products obtained in the above condensation are his (polyoxyalkylene) tallowamines represented by the formula Ta1lowN (CHzCHgO). CI-ht JHO H 2 TABLE III Conductivity of I-Decene-Maleic Anhydride-SO Terpolymer Arquad" ZC-Nitrite Composition Concentration lb/IOOO Active Ingredients (ppm) Conductivity Additive bbl Polysulfone Quaternary C.U.

A. Fuel: Bayol I. polysulfone" I I 0 O 5 2. Iolysulfone 3 3 I) I) 5 3. "Arquad" 2(,'-

Nitrit 3 (I 8.4 It) 4. Invention Composition I I ().I 70 5. Invention Composition 3 2.9 0.3 I

Fuel: BayoI/Tolucne (SS/I5) B. l. Polysulfonc I I 0 5 2. Polysulfone 3 3 0 I5 3. "Arquud" 2C- Nitrite 3 0 8.4 I05 4. Invention Composition 3 2.9 0.3 I75 5. Invention Composition 3 2.9 0.3 I75 Concentration Ih/IOOO Active Ingredients (ppm) Conductivity Additive bbl Polysulfone Quaternary C.U.

C. Fuel: No. 2 Fuel Oil I. Polysulfone l I 0 2. Polysulfonc 3 3 0 I00 3. Arqu-ad" 2C- Nitrite 3 0 8.4 5 4. Invention Composition I I O.I 7O 5. Invention Composition 3 2.9 0.3 I35 l-dcccne maleie anhydride-SO, terpolymcr of Ex. I). 25% in toluene. dicocodimethylammonium nitrite. in isopropanol. 25:I combination of" and (24; polysulfone and 2.771 quaternary).

The quaternary ammonium compounds were:

Tallow-N (CHQGHIO) CHIHO 1H gCH SO4 B. CH:

C. CH:

Tallow-N (CHiCH O), CHzHO 4 1011380;

For the preparation of the composition, each of the above quaternary ammonium. compounds (2 g.) was added to 50 g. portionsofa solution of l-decene polysulfone (25%) in toluene. The results of conductivity measurements in two fuels are shown in Table N below.

TABLE IV Conductivity of l-Decene Polysulfone/Quaternary Compounds Containing Polyoxyalkylene Groups Concentration lb/lOOO Active lngredients(ppm) Conductivity Additive bbl Polysulfone Quaternary C.U.

Fuel: Bayol A 3 I2 25 B 3 0 I2 20 C 3 0 l2 l5 Polysulfone 3 3 0 5 Invention Composition Containing A 3 3 0.5 50 Invention I Composition Containing B 3 3 0.5 95 Invention Composition Containing C 3 3 0.5 160 Fuel: No. 2 Fuel Oil 3 0 12 25, a 3 0 I2 55 C 3 0 l2 55 Polysullone I0 l0 0 30 Invention Composition Containing A 3 3 0.5 80 Invention Composition Containing B 3 3 0.5 90 lnvention Composition Containing C 3 3 0.5 105 The above data again show that unexpected conductivities are obtained when olefin polysulfones arecombined with quaternary ammonium compounds containing polyoxyalkylene substituents on the quaternary nitrogen.

EXAMPLE 26 I This example shows increased conductivities effected 18 by a composition of an olefin polysulfone and quaternary ammonium compounds of the lecithin class. Lecithins are glycerides in which one of the fatty acids at either the a or [3 position is replaced by a residue composed of phosphoric acid and a base. Lecithins used in this example were commercial products. Lecithin A was a liquid product while Lecithin B was a solid. For the combination, 5 g. of the lecithin was dissolved in 50 g. of a 25 percent solution of l-decene polysulfone in toluene. The conductivity data are summarized in Table V below.

TABLE v Conductivity of l-Decene Polysulfone With Lecithins Fuel: Bayol Concentrations lb/IOOO Active lngredients(ppm) Conductivity Additive bbl Polysulfone Quaternary .U.

Lecithin A 3 0 l2 lOO Lecithin B 3 0 I2 I Polysulfone 3 3 0 5 Polysulfone Lecithin A 3 3 L2 Polysulfone Lecithin B 3 3 1.2 200 These results show that the conductivities obtained with the compositions of olefin polysulfones and quaternary ammonium'compounds of the lecithin-type are considerably greater than those expected from the individual effects.

EXAMPLE 27 This example shows the increased electrical conductivity of fuel oils and diesel fuels treated with a composition of this invention. The example also illustrates the unexpected increase in the conductivities of the treated fuels with time. The composition used herein was that of --decene polysulfone and dicocodimethylammonium nitrite prepared by combining 25 parts of the l-decene polysulfone (25%) solution in toluene with 1 part of Arqua'd 2C-Nitrite (70%) solution in isopropanol.

The combination therefore contained 24 percent 1- decene polysulfone and 2.7 percent dicocodimethylammonium nitrite in a mixture of toluene and isporopanol. The tests were carried out by treating the fuels with an amount of the composition which would provide initial conductivity of at least about 50 conductivity units (C.U.) or at least about 200 conductivity units. For comparative purposes, data for two commercially available antistatic additives, designated A and B are also included. Commercial Additive A was a 50 percent solution in a hydrocarbon solvent of a mixture of chromium salts of mono and dialkyl salicylic acid, calcium dodecylsulfosuccinate and a basic polymer while Commercial Additive B was a polymeric amine salt (50 percent in hydrocarbon). The conductivity values were determined with a Maihak Conductivity Indicator as described previously. The test samples were stored in metal containers at room temperature and the conductivities were determined at stated intervals. The results are summarized in Table VI below.

TABLE VI Fuel Oil Conductivity Concentration Active Fuel and lb/IOOO Ingredient Conducnvlty (CUJ 7: Change Additive bbl ppm Initial I Wk. 3 Wk. 6 Wk. at 6 Wk.

Fuel A, No. 2 Fuel Oil (C.U.=20) Invention Composition 0.25 0.27 75 I15 I10 125 6 Invention Composition 2.0 2.2 195 265 250 230 18 Comm. Additive A 1.0 2.0 205 260 220 220 7 Comm. Additive B 0.5 1.0 180 I 70 80 55 Fuel B, No.2 Diesel Fuel (C.U.=0) Invention Composition 0.5 0.54 I00 I15 125 150 Invention Composition 7.0 7.6 180 340 385 405 125 Comm. Additive A 3.0 6.0 230 300 310 340 48 Comm. Additive B 9.0 18.0 200 210 I90 225 13 Fuel C No. 2 Diesel Fuel (C.U.=0I Invention Composition I.0 I.I 50 I65 I50 I90 280 Invention Composition 10.0 10.8 130 325 375 460 254 ('omm. Additive A 1.25 2.5 205 280 225 250 22 ('omm. Additive II 7.0 14.0 205 210 200 240 I7 Fuel I), No. 2 Fuel Oil (('.ll.=0) Invention Composition 0.25 0.27 55 70 85 r 55 Invention Composition 10.0 10.8 210 280 360 460 120 Comm. Additive A 1.5 3.0 220 160 165 I90 14 Comm. Additive I3 5.0 10.0 200 95 80 60 Fuel F No. 2 Fuel Oil (C.U.=0) Invention Composition 5.0 5.4 50 I20 I50 200 300 Comm. Additive A 1.0 2.0 190 I I60 I90 0 Comm. Additive B 10.0 20.0 190 I 140 180 5 Fuel F, No. I Fuel Oil (C.Ul=30) Invention Composition 0.125 0.14 200 230 250 240 20 Comm. Additive A 0.5 1.0 215 200 I40 35 Comm. Additive B 0.25 0.5 215 90 55 74 Fuel G, No. 2 Fuel Oil (C.U.=I5) Invention Composition 0.25 0.27 440 510 600 650 Invention Composition 1.25 I35 I 1000+ 1000+ 1000+ 425 Comm. Additive A 0.25 0.5 50 Comm. Additive B 0.75 I 5 55 173 Fuel H, No. 2 Fuel Oil (C.U.= 0) Invention Composition 0.125 0.14 65 I05 I25 145 123 Invention Composition 1.0 1.08 225 260 315 350 55 Comm. Additive A 1.0 2.0 195 270 255 265 36 Comm. Additive B 2.5 5.0 210 I55 215 13 Fuel 1, No. 2 Fuel Oil (C.U.= 0) Invention Composition [.0 1.08 50 345 720 1340 Invention Composition 3.0 3.24 2I5 1000+ 1000+ 1000+ 365 Comm. Additive A 0.5 1.0 290 100 85 80 72 Comm. Additive B 5.0 10.0 275 260 225 265 4 The data in the above table demonstrate the variability in response of fuels to antistatic additives. The

above data also show that the compositions of the presso stances, the conductivity either remained about the,

same or decreased. It is also to be noted that in fuels wherein the Commercial Additives showed an increase in conductivity with time, the increase in conductivity exhibited by the composition of the invention was considerably higher. The difference in increased conductivity is clearly shown by comparing the figures in the last column of the table %Change at 6 Weeks).

EXAMPLE 28 This example shows increased electrical conductivities of commercial jet fuels when a small amount of a 55 composition of the invention is dissolved therein. The

invention composition used herein is the same as described in the Example 27. The tests were carried out with a sample of .IP-S, two samples of .lP-4 (designated .IP-4(A) and JP-4(B), a sample jet kerosene and two 60 samples of turbine fuels (designated Turbine Fuel (A) and Turbine Fuel (8)). The conductivity measurements were carried out as described previously. The test samples were stored in metal containers at room temperature and the conductivities were determined at 65 stated intervals. The results are shown in Table VII below.

TABLE VII Jet Fuel Conductivity Additive Combination: I Additive Concentration 25 parts l-decene polysulfone (25%) in toluene plus 1 part dicocodimethylammonium nitrite (70%) in isopropanol.

Conductivity (C.U.)

Active Ila/I000 Ingredients Change bbl (ppm) Fuel Initial 3 Wks. 6 Wks. 6 Wks.

O .IP-4(A) IO 0,125 0.13 JP-4(A) I25 620 800 540 0.25 0.27 JP-4(A) I80 650 750 317 0 0 JP- l0 0.5 0.54 .IP-5 50 95 135 I70 0 0 JP-4(B) 0 L0 1.08 .IP-4(B) 40 I50 75 87 3.0 3.2 .IP-4(B) 215 I25 145 33 0 0 Turb. Fuel(A) l0 0.25 0.27 Turb. Fuel(A) 50 I55 210 320 4.0 4.3 Turb. Fuel(A) I90 225 255 34 0 0 Jet Kern. L0 1.08 Jet Kcro. 50 85 J00 I00 60 6.5 Jet Kcro. 210 200 220 5 (l 0 Turb. Fuel(B) 10 1.25 1.35 Turb. Fuel(B) S0 85 I00 I00 7.0 7.6 Turb. Fuel(B) 230 275 290 26 The above data again show the variability in response of the hydrocarbon fuels to antistatic additives. The

above data, however, clearly show increased conduc- EXAMPLE 29 This example shows the excellent separation from water of fuels containing a composition of the invention. In use of hydrocarbon fuels, particularly jet fuels, it is essential that after any contact with water, such hydrocarbon fuels separate themselves from water rapidly. The test for water separation was carried out according to ASTM D 2550-66T. In this test, WSIM (Water Separation Index, Modified) is measured with an ASTM -CRC Water Separometer, a device in which a fuel-water emulsion is prepared and metered through a cell containing a standardized glass fiber coalescer. The cell effluent turbidity, due to entrained water, is measured by light transmission through the fuel to a photocell. The output of the photocell is fed to a meter with a 0 to I00 scale, from which the numerical rating of the fuel is read. The higher the number, the more readily does the fuel release water. Usually WSIM rating of about 70 or higher is considered to be satisfactory. The composition of the invention used was a mixture of 25 parts of l-decene polysulfone (25 percent in toluene) and 1 part, of dicocodimethylammonium nitrite (70 percent) inisopropanol. The jet fuels used were JP-4(A) and JP-5 as used in Example 28. (Example 28 showed that this composition at 0.125 lb'/ 1000 bbl and at 0.25 lb/ 1000 bbl gave conductivities of C.U. and 180 C.U. in JP-4(A) and at 0.5 lb/l000 bbl in .lP-5

gave a conductivity of 50 C .U.) The results are summa-.

rized below in Table VIII.

TAB E VIII WSIM VALUES (ASTM D2550) The above data snow that'the composition of the invention in use range concentration has no adverse effect upon the water separation characteristics of the base jet fuels.

EXAMPLE 30 This example shows increased conductivities for hydrocarbon fuels with a combination of an olefin polysulfone and a quaternary ammonium compound of the betaine type. A concentrate of N-lauryl betaine (i.e. N- lauryl-N,N-dimethylglycine), 25 weight percent in toluene, was prepared. Olefin polysulfone used was 1- decene polysulfone (25%) in toluene. These concentrates were added to two different hydrocarbon fuels to give the concentrations of active ingredients as indicated. The conductivity data obtained are shown in Table IX below.

TABLE IX The above results show that with the composition of an olefin polysulfone and a quaternary ammonium compound of the betaine type, increased conductivities are obtained.

The foregoing detailed description has been given for clarity of understanding only and no unnecessary 1imitations are to be understood therefrom. The invention is not limited to exact details shown and described for obvious modifications will occur to one skilled in the art.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An antistatic composition comprising, in a ratio of 100:1 to 1:100,

l. a polysulfone copolymer consisting essentially of a. about 50 mol percent of units from sulfur dioxide,

b. from about 40 to about 50 mol percent of units derived from a l-alkene or mixture of l-alkenes having from about 6 to 24 atoms,

c. from to about mol percent of units derived from an olefin having the formula wherein A is a group having the formula (C,H )COOl-l wherein x is from 0 to about 17, and B is hydrogen or carboxyl, with the proviso that when B is carboxy1,x is 0 and wherein A and B together may be a dicarboxylic anhydride group, and

2. a quaternary ammonium compound having the wherein R and R are the same or different alkyl groups having from 1 to 22 carbon atoms; R is selected from the group consisting of alkyl groups having from 1 to 22 carbon atoms and group wherein R is hydrogen or methyl and n is from 1 to cl. a

group wherein R and R are the same or different alkyl groups having from 1 1 to 19 carbon atoms; and

e. a R CO{ group wherein R is a hydrocarbyl group having from 1 to 17 carbon atoms;

with the proviso that when R, R, R and R are each alkyl groups, at least one of R, R, R and R is an alkyl group having at least 8 carbon atoms; A is an anion; z is 0 or 1 and when R is (d) or (e), z is 0; y is at least one and when z is 1, y is numerically equal to the ionic valence of anion A.

2. An antistatic composition according to claim 1 wherein the weight ratio of polysulfone copolymer.( 1 and quaternary ammonium compound (2) is from :1 to 1:100.

3. An antistatic composition according to claim 2 wherein the polysulfone copolymer 1) consists essentially of a. about 50 mol percent of units derived from sulfur dioxide, and

b. about 50 mol percent of units derived from a 1- olefin having from 8 to 12 carbon atoms. 4. An antistatic composition according to claim 3 wherein the quaternary ammonium compound (2) has wherein R is methyl, R is an alkyl group having from 8 to 22 carbon atoms and each of R and R is a laiiolfi group wherein the sum of a and b is from 1 to 20.

6. An antistatic composition according to claim 3 wherein the quaternary ammonium compound 2) has the formula 1 T- Am (y) wherein each of R', R and R is methyl and R is a group, wherein each of R and R is an alkyl group having from 11 to 19 carbon atoms.

7. An antistatic composition according to claim 3 wherein the quaternary ammonium compound 2) has the formula wherein each of R and R is methyl, R is an alkyl group having from 8 to 22 carbon atoms and R is a CH CO' group.

8. An antistatic composition according to claim 4 wherein the polysulfone copolymer (1) is l-decene polysulfone and the quaternary ammonium compound (2) is dicocodimethylammonium nitrite.

9. An antistatic composition according to claim 2 wherein the polysulfone copolymer has a molecular weight of from about 50,000 to about 900,000.

10. A hydrocarbon fuel comprising A. a liquid hydrocarbon boiling in the range of from about 70 F. and about 700F., and

B. an antistatic amount of a composition comprising 1. a polysulfone copolymer consisting essentially of a. about 50 mol percent of units derived from sulfur dioxide,

b. from about 40 to about 50 mol percent of units derived from a l-alkene or mixture of lalkenes having from about 6 to 24 carbon atoms,

wherein the polysulfone copolymer has an average molecular weight of between X and 9 X 10 and c. from'0 to about 10 mol percent of units derived from an olefin having the formula wherein A is a group having the formula (C1H )-COOH wherein x is from 0 to about l7, and B is hydrogen or carboxyl, with the proviso that when B is carboxyl, x is 0 and wherein A and B together may be a dicarboxylic anhydride group, and 2. a quaternary ammonium compound having the formula wherein R and R are the same or different alkyl groups having from 1 to 22 carbon atoms; R is selected from the group consisting of alkyl groups having from 1 to 22 carbon atoms .and

groups wherein R is hydrogen or methyl and n is from 1 to 20; and R is selected from the group consisting of a. an alkyl group having from 1 to 22 carbon atoms;

b. an aralkyl group having from 7 to 22 carbon atoms;

'froup wherein R is hydrogen or methyl and n is from l to 20; d. a

0 l -omcHrooomcmoooaucmooow group wherein R and R are the same or different alkyl groups having from 11 to 19 carbon atoms; and e. a -R CO{ group wherein R is a hydrocarbyl group having from 1 to 17 carbon atoms; with the proviso that when R, R R and R are each alkyl groups, at least one of R, R, R and R is an alkyl group having at least 8 carbon atoms; A is an anion; z is 0 or 1 and when R is (d) or (e), z is 0; y is at least one and when 2 is l, y is numerically equal to the ionic valence of anion A.

@ 0 UNI ED STA'IES. PATENT OFFECE CERTIFICATE 0F CURRECTKQN Patent no 3, 1,8 +8 Dated Ma 21, 1W4

Inveotofls) Daniel Do n SOn It is certified that error appears: in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

51am 53 column 2 4-, line as "the formula should read (CH CH2) (CH CH0) H Claim 10, column 26, line 2, "froup" should be group I Signed one seeled rhis 29th dey' of October 1974.

(SEAL) Attest McCOY M. mason 'JR. Arresting Officer 0. MARSHALL DANN Commissioner of Patents 

1. OLEFIN-SULFUR DIOXIDE COPOLYMER CONSISTING ESSENTIALLY OF UNITS DERIVED FROM SULFUR DIOXIDE, C6-1-ALKENE, AND OPTIONALLY AN OLEFIN HAVING THE FORMULA
 2. a quaternary ammonium compound having the formula
 2. A QUATERNARY AMMONIUM COMPOUND.
 2. a quaternary ammonium compound having the formula -
 2. An antistatic composition according to claim 1 wherein the weight ratio of polysulfone copolymer (1) and quaternary ammonium compound (2) is from 100:1 to 1:100.
 3. An antistatic composition according to claim 2 wherein the polysulfone copolymer (1) consists essentially of a. about 50 mol percent of units derived from sulfur dioxide, and b. about 50 mol percent of units derived from a 1-olefin having from 8 to 12 carbon atoms.
 4. An antistatic composition according to claim 3 wherein the quaternary ammonium compound (2) has the formula
 5. An antistatic composition according to claim 3 wherein the quaternary ammonium compound (2) has the formula
 6. An antistatic composition according to claim 3 wherein the quaternary ammonium compound (2) has the formula
 7. An antistatic composition according to claim 3 wherein the quaternary ammonium compound (2) has the formula
 8. An antistatic composition according to claim 4 wherein the polysulfone copolymer (1) is 1-decene polysulfone and the quaternary ammonium compound (2) is dicocodimethylammonium nitrite.
 9. An antistatic composition according to claim 2 wherein the polysulfone copolymer has a molecular weight of from about 50,000 to about 900,000.
 10. A hydrocarbon fuel comprising A. a liquid hydrocarbon boiling in the range of from about 70*F. and about 700*F., and B. an antistatic amount of a composition comprising 